Chemical and isotopic compositions of authigenic carbonates from the area of the Sakhalin-Deryugin gas anomaly, Sea of Okhotsk

Features of sedimentation of carbonate mineral associations in the northeastern shelf of Sakhalin and other regions of the Sea of Okhotsk are considered. Special attention is paid to correlation between carbonate neoformations and abnormal fluxes of methane. In bottom sediments with high contents of methane carbonate-sulfide associations occur, their generation has been influenced by gas (mostly methane) fields. Joint consideration of distribution of gas and geochemical fields and mineral associations in the Sea of Okhotsk allows to understand better a mechanism of mineral generation in bottom sediments, possible formation of ore accumulations, and to use them as indicators for prognosis of mineral resources.

Gas hydrates at DSDP Leg 84

On DSDP Leg 84, gas hydrates were found at three sites (565, 568, and 570) and were inferred, on the basis of inorganic and organic geochemical evidence, to be present at two sites (566 and 569); no evidence for gas hydrates was observed at Site 567. Recovered gas hydrates appeared as solid pieces of white, icelike material occupying fractures in mudstone or as coarse-grained sediment in which the pore space exhibited rapid outgassing. Also a 1.05-m-long core of massive gas hydrate was obtained at Site 570. Downhole logging indicated that this hydrate was actually 3 to 4 m thick. Measurements of the amount of methane released during the decomposition of these recovered samples clearly showed that gas hydrates had been found. The distribution of evolved hydrocarbon gases indicated that Structure I gas hydrates were present because of the apparent inclusion of methane and ethane and exclusion of propane and higher molecular weight gases. The water composing the gas hydrates was fresh, having chlorinities ranging from 0.5 to 3.2 per mil. At Sites 565, 568, and 570, where gas hydrates were observed, the chlorinity of pore water squeezed from the sediment decreased with sediment depth. The chlorinity profiles may indicate that gas hydrates can often occur finely dispersed in sediments but that these gas hydrates are not recovered because they do not survive the drilling and recovery process. Methane in the gas hydrates found on Leg 84 was mainly derived in situ by biogenic processes, whereas the accompanying small amounts of ethane likely resulted from low-temperature diagenetic processes. Finding gas hydrates on Leg 84 expands observations made earlier on Leg 66 and particularly Leg 67. The results of all of these legs show that gas hydrates are common in landward slope sediments of the Middle American Trench from Mexico to Costa Rica.

Maxima of interstitial water and gas parameters in ODP Leg 182 sediments

During the drilling of the southern Australian continental margin (Leg 182 of the Ocean Drilling Program), fluids with unusually high salinities (to 106?) were encountered in Miocene to Pleistocene sediments. At three sites (1127, 1129, and 1131), high contents of H2S (to 15%), CH4 (50%), and CO2 (70%) were also encountered. These levels of H2S are the highest yet reported during the history of either the Deep Sea Drilling Project or the Ocean Drilling Program. The high concentrations of H2S and CH4 are associated with anomalous Na+/Cl- ratios in the pore waters. Although hydrates were not recovered, and despite the shallow water depth of these sites (200-400 m) and relative warm bottom water temperatures (11-14°C), we believe that these sites possess disseminated H2S-dominated hydrates. This contention is supported by calculations using the measured gas concentrations and temperatures of the cores, and depths of recovery. High concentrations of H2S necessary for the formation of hydrates under these conditions were provided by the abundant (SO4)2- caused by the high salinities of the pore fluids, and the high concentrations of organic material. One hypothesis for the origin of these fluids is that they were formed on the adjacent continental shelf during previous lowstands of sea level and were forced into the sediments under the influence of hydrostatic head.

Surface in situ measurements of atmospheric CO, CH4, and CO2 combined with selected meteorological measurements at the University of Wollongong, Australia

Wollongong, Australia is an urban site at the intersection of anthropogenic, biomass burning, biogenic and marine sources of atmospheric trace gases. The location offers a valuable opportunity to study drivers of atmospheric composition in the Southern Hemisphere. Here, a record of surface carbon monoxide (CO), methane (CH4) and carbon dioxide (CO2) was measured with an in situ Fourier transform infrared trace gas analyser between April 2011 and August 2014. Clean air was found to arrive at Wollongong in approximately 10% of air masses. Biomass burning influence was evident in the average annual cycle of clean air CO during austral spring. A significant negative short-term trend was found in clean air CO (-1.5 nmol/mol/a), driven by a reduction in northern Australian biomass burning. Significant short-term positive trends in clean air CH4 (5.4 nmol/mol/a) and CO2 (1.9 ?mol/mol/a) were consistent with the long-term global average trends. Polluted Wollongong air was investigated using wind-direction/wind-speed clustering, which revealed major influence from local urban and industrial sources from the south. High values of CH4, with anthropogenic DCH4/DCO2 enhancement ratio signatures, originated from the northwest, in the direction of local coal mining. A pollution climatology was developed for the region using back trajectory analysis and DO3/DCO enhancement ratios. Ozone production environments in austral spring and summer were associated with anticyclonic meteorology on the east coast of Australia, while ozone depletion environments in autumn and winter were associated with continental transport, or fast moving trajectories from southern latitudes. This implies the need to consider meteorological conditions when developing policies for controlling air quality.

Simulated change in atmospheric CO2 and D14C around 14.6 kyr BP, at the onset of the northern hemispheric warming into the Bølling/Allerød

One of the most abrupt and yet unexplained past rises in atmospheric CO2 (10 p.p.m.v. in two centuries) occurred in quasi-synchrony with abrupt northern hemispheric warming into the Bølling/Allerød, 14,600 years ago. Here we use a U/Th-dated record of atmospheric D14C from Tahiti corals to provide an independent and precise age control for this CO2 rise. We also use model simulations to show that the release of old (nearly 14C-free) carbon can explain these changes in CO2 and D14C. The D14C record provides an independent constraint on the amount of carbon released (125 Pg C). We suggest, in line with observations of atmospheric CH4 and terrigenous biomarkers, that thawing permafrost in high northern latitudes could have been the source of carbon, possibly with contribution from flooding of the Siberian continental shelf during meltwater pulse 1A. Our findings highlight the potential of the permafrost carbon reservoir to modulate abrupt climate changes via greenhouse-gas feedbacks.

Carbon isotopic composition and dissolved CO2 concentration in pore waters of ODP Leg 174A sites

Microbially mediated redox diagenetic processes in marine sediments are reflected in the amount and carbon isotopic composition of dissolved CO2 and CH4 (Claypool and Kaplan, 1974). Oxidation of organic matter gives rise to dissolved CO2 with about the same 13C/12C ratio as the starting organic matter. Subsequent reduction of CO2 to form CH4 involves a large (~70) kinetic isotopic effect, resulting in significant 13C depletion in the CH4, and 13C enrichment in the residual CO2. Ocean Drilling Program Leg 174A (offshore New Jersey) presented an opportunity to study these processes in shelf and upper slope sediments. Holes 1071A-1071D, 1071F, and 1072A were drilled on the shelf in water depths of 88.0-98.1 m. Hole 1073A was drilled on the slope in 639.4 m of water. Pore-water samples were collected for analysis at all three sites, whereas gas samples could only be obtained from Hole 1073A on the slope.

Gas content, composition of gas hydrate and volumetric gas/water ratios of ODP and DSDP sites

Gas hydrate samples were recovered from four sites (Sites 994, 995, 996, and 997) along the crest of the Blake Ridge during Ocean Drilling Program (ODP) Leg 164. At Site 996, an area of active gas venting, pockmarks, and chemosynthetic communities, vein-like gas hydrate was recovered from less than 1 meter below seafloor (mbsf) and intermittently through the maximum cored depth of 63 mbsf. In contrast, massive gas hydrate, probably fault filling and/or stratigraphically controlled, was recovered from depths of 260 mbsf at Site 994, and from 331 mbsf at Site 997. Downhole-logging data, along with geochemical and core temperature profiles, indicate that gas hydrate at Sites 994, 995, and 997 occurs from about 180 to 450 mbsf and is dispersed in sediment as 5- to 30-m-thick zones of up to about 15% bulk volume gas hydrate. Selected gas hydrate samples were placed in a sealed chamber and allowed to dissociate. Evolved gas to water volumetric ratios measured on seven samples from Site 996 ranged from 20 to 143 mL gas/mL water to 154 mL gas/mL water in one sample from Site 994, and to 139 mL gas/mL water in one sample from Site 997, which can be compared to the theoretical maximum gas to water ratio of 216. These ratios are minimum gas/water ratios for gas hydrate because of partial dissociation during core recovery and potential contamination with pore waters. Nonetheless, the maximum measured volumetric ratio indicates that at least 71% of the cages in this gas hydrate were filled with gas molecules. When corrections for pore-water contamination are made, these volumetric ratios range from 29 to 204, suggesting that cages in some natural gas hydrate are nearly filled. Methane comprises the bulk of the evolved gas from all sites (98.4%-99.9% methane and 0%-1.5% CO2). Site 996 hydrate contained little CO2 (0%-0.56%). Ethane concentrations differed significantly from Site 996, where they ranged from 720 to 1010 parts per million by volume (ppmv), to Sites 994 and 997, which contained much less ethane (up to 86 ppmv). Up to 19 ppmv propane and other higher homologues were noted; however, these gases are likely contaminants derived from sediment in some hydrate samples. CO2 concentrations are less in gas hydrate than in the surrounding sediment, likely an artifact of core depressurization, which released CO2 derived from dissolved organic carbon (DIC) into sediment. The isotopic composition of methane from gas hydrate ranges from d13C of -62.5 per mil to -70.7 per mil and dD of -175 per mil to -200 per mil and is identical to the isotopic composition of methane from surrounding sediment. Methane of this isotopic composition is mainly microbial in origin and likely produced by bacterial reduction of bicarbonate. The hydrocarbon gases here are likely the products of early microbial diagenesis. The isotopic composition of CO2 from gas hydrate ranges from d13C of -5.7 per mil to -6.9 per mil, about 15 per mil lighter than CO2 derived from nearby sediment.

Consistent increase in dimethyl sulfide (DMS) in response to high CO2 in five shipboard bioassays from contrasting NW European waters

The ubiquitous marine trace gas dimethyl sulfide (DMS) comprises the greatest natural source of sulfur to the atmosphere and is a key player in atmospheric chemistry and climate. We explore the short-term response of DMS production and cycling and that of its algal precursor dimethyl sulfoniopropionate (DMSP) to elevated carbon dioxide (CO2) and ocean acidification (OA) in five 96 h shipboard bioassay experiments. Experiments were performed in June and July 2011, using water collected from contrasting sites in NW European waters (Outer Hebrides, Irish Sea, Bay of Biscay, North Sea). Concentrations of DMS and DMSP, alongside rates of DMSP synthesis and DMS production and consumption, were determined during all experiments for ambient CO2 and three high-CO2 treatments (550, 750, 1000 µatm). In general, the response to OA throughout this region showed little variation, despite encompassing a range of biological and biogeochemical conditions. We observed consistent and marked increases in DMS concentrations relative to ambient controls (110% (28-223%) at 550 µatm, 153% (56-295%) at 750 µatm and 225% (79-413%) at 1000 µatm), and decreases in DMSP concentrations (28% (18-40%) at 550 µatm, 44% (18-64%) at 750 µatm and 52% (24-72%) at 1000 µatm). Significant decreases in DMSP synthesis rate constants (µDMSP /d) and DMSP production rates (nmol/d) were observed in two experiments (7-90% decrease), whilst the response under high CO2 from the remaining experiments was generally indistinguishable from ambient controls. Rates of bacterial DMS gross consumption and production gave weak and inconsistent responses to high CO2. The variables and rates we report increase our understanding of the processes behind the response to OA. This could provide the opportunity to improve upon mesocosm-derived empirical modelling relationships and to move towards a mechanistic approach for predicting future DMS concentrations.

Gas hydrates of the Gulf of Mexico

Gas hydrates were recovered from eight sites on the Louisiana slope of the Gulf of Mexico. The gas hydrate discoveries ranged in water depths from 530 to 2400 m occurring as small to medium sized (0.5-50 mm) nodules, interspersed layers (1-10 mm thick) or as solid masses (> 150 mm thick). The hydrates have gas:fluid ratios as high as 170:1 at STP, C1/(C2 + C3) ratios ranging from 1.9 to > 1000 and d13C ratios from -43 to -71 per mil. Thermogenic gas hydrates are associated with oil-stained cores containing up to 7% extractable oil exhibiting moderate to severe biodegradation. Biogenic gas hydrates are also associated with elevated bitumen levels (10-700 ppm). All gas hydrate associated cores contain high percentages (up to 65%) of authigenic, isotopically light carbonate. The hydrate-containing cores are associated with seismic "wipeout" zones indicative of gassy sediments. Collapsed structures, diapiric crests, or deep faults on the flanks of diapirs appear to be the sites of the shallow hydrates.

A high-resolution record of the atmospheric CO2 concentration from 60-20 kyr BP from the Taylor Dome ice core, Antarctica

A high-resolution record of the atmospheric CO2 concentration from 60 to 20 thousand years before present (kyr BP) based on measurements on the ice core of Taylor Dome, Antarctica is presented. This record shows four distinct peaks of 20 parts per million by volume (ppmv) on a millennial time scale. Good correlation of the CO2 record with temperature reconstructions based on stable isotope measurements on the Vostok ice core (Antarctica) is found.

Geochemistry of gas hydrates of DSDP Hole 84-570

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4°C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ~0.2% ethane, and ~0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 per mil, relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift.